Patent GB-446411-A (GB)
Title: A process for manufacturing halogenated hydrocarbons
IPC: C07C17/02
Filed: 1936-01-18
Abstract: Addition of halogen to unsaturated hydrocarbons is effected in the presence of one or more complex cyanides as catalyst. Cyanides containing metals of Groups 1, 2, 3 or 8 of the periodic system, particularly Cu, Zu, Al or Fe, are specified, e.g. alkali or alkaline earth ferroor ferri-cyanides, potassium nickel, potassium cadmium, or potassium zinc cyanides, potassium cuprocyanide, or cupro-cupricyanide.  They may be combined with metal chlorides, e.g. aluminium, ferric or chromium chloride.  The components can be mixed dry, or dissolved in water and the solution evaporated.  In this case reaction may occur, thus K4Fe(CN)6 and AlCl3 give KAlFe(CN)6 and KCl. Carriers such as pumice stone, active carbon or silica gel may be used, and the contact mass may be dried and preheated before use. The process is adapted to the manufacture of 1,2-dichlorethane, propane and the like from the corresponding alkenes, and also comprises halogenation of hydrocarbons with more than one double bond or with triple bonds, and addition of halogens other than chlorine. The unsaturated hydrocarbons may be in admixture with other compounds as in cracking gases, oil, coal or coke furnace gas.  The presence of a small quantity of water vapour is desirable.  Reaction is carried out in the liquid or vapour phase and pressure is normal, reduced, or elevated, e.g. 3 or more atmospheres.  The temperature is generally not above 250 DEG  C.  The halogen compounds may be separated by cooling, with adsorbents, or with solvents.  According to examples: (1) an ethene fraction obtained by low temperature fractionation of coke furnace gas and containing 12,4 per cent ethene and 1,4 per cent propene is passed through a wetting chamber and then through a contact furnace containing a catalyst obtained by evaporating a solution of K4Fe(CN)6, AlCl3, and FeCl3. Chlorine is introduced simultaneously.  The intake temperature is 15 DEG  C. and that at \ba1/3\be and \ba2/3\be of the height is 80 and 135 DEG  C. respectively; (2) the same ethene fraction is moistened, mixed with chlorine, and passed at room temperature over a catalyst prepared from a solution of K3Cu(CN)4 and an equimolecular quantity of FeCl3 + AlCl3.  The potassium cuprocyanide may be replaced by potassium zinc cyanide, sodium ferrocyanide, or cupri - cuprocyanide, or the aluminium chloride by potassium chloride.ALSO:Catalysts for halogenating unsaturated hydrocarbons comprise one or more complex cyanides.  Cyanides containing metals of Groups 1, 2, 3 or 8 of the periodic system, particularly Cu, Zn, Al, or Fe are specified, e.g. alkali or alkaline earth ferro- or ferricyanides, potassium nickel, potassium cadmium, or potassium zinc cyanides, potassium cuprocyanide, cuprocupricyanide, or cupricuprocyanide.  They may be combined with metal chlorides, e.g. aluminium, ferric or chromium chloride.  The components can be mixed dry, or dissolved in water and the solution evaporated. In this case reaction may occur, thus K4Fe(CN)6 + AlCl3 give KAlFe(CN)6 and KCl.  Carriers such as pumice stone, active carbon or silica gel may be used, and the contact mass may be dried and preheated before use.